Golf balls comprising chiral diols or chiral cyclic ethers

ABSTRACT

A golf ball comprising a core and a cover, wherein the core or the cover comprises a thermoplastic or thermoset composition comprising a polyurea prepolymer formed from a reactant A comprising an isocyanate; and a reactant B comprising a polyether polyamine having a repeating branched oxyalkylene monomer unit, or a polymerized polyamine formed from a chiral diol or a chiral cyclic ether.

FIELD OF THE INVENTION

The present invention relates to golf balls, and more particularly tonovel compositions for a golf ball that comprises a polymerized polyahlformed from a chiral diol or a chiral cyclic ether.

BACKGROUND OF THE INVENTION

The United States Golf Association (“USGA”) provides five (5)regulations to keep golf balls consistent. Specifically, the golf ballmust weigh no more than 1.62 ounces and measure no less than 1.68 inchesin diameter. The initial velocity of the ball as tested on a USGAmachine at a set club head speed must not exceed 255 ft/sec. The overalldistance of the ball as tested with a USGA specified driver at 160ft/sec and a 10-degree launch angle must not exceed 296.8 yards.Furthermore, the ball must pass a USGA-administered symmetry test.Within the confines of these regulations, other performancecharacteristics of the ball, including distance, durability, feel, spin,sound, and the like may be modified through alterations in materialcompositions, constructions, diameters and/or thickness, and surfaceconfigurations of various portions of the ball, such as the core, thecover, and intermediate layer(s) therebetween. Other physical,mechanical, chemical, and/or optical properties of the portions,including color stability, compression, density, flexural modulus, gasor vapor permeability, hardness, stiffness, tear resistance, weight, andthe like may also be affected by these alterations.

Conventional cover or intermediate layer materials for golf ballsinclude ionomer resins and polyurethanes. Chemically, ionomer resins area copolymer of an olefin and an ethylenically unsaturated α,β-carboxylicacid having 10 to 100 percent of the carboxylic acid groups neutralizedby a metal ion. Polyurethanes are typically formed from a prepolymer ofpolyol with isocyanate and a curing agent. Ionomer covers are virtuallycut-proof, but they provide inferior spin and feel to the golf balls.Conventional polyurethane covers generally afford excellent feel andgood durability, but not resilience or light stability comparable toionomer covers.

Polyurea has also been proposed as cover materials for golf balls. Forinstance, U.S. Pat. No. 5,484,870 discloses a polyurea compositioncomprising the reaction product of an organic diisocyanate and anorganic amine. Like polyurethanes, polyurea is not completely comparableto ionomer covers with respect to resilience. Therefore, there remains acontinuing need for golf ball materials and compositions with superiorresistance to cut, scratch, abrasion, discoloration, moisture, and otherwearing and weathering elements, that provide improved performancecharacteristics such as resilience and feel.

SUMMARY OF THE INVENTION

The present invention is directed to a golf ball having a core and acover, at least one of which comprises a thermoplastic or thermosetcomposition of a polyurethane prepolymer or polyurea prepolymer formedfrom a reactant A comprising an isocyanate, and a reactant B comprisingpolymerized polyahl (polymerized polyol or polymerized polyamine,respectively). The polymerized polyol is preferably a polymerizationproduct of a chiral diol or chiral cyclic ether, or a polyether polyolhaving a repeating branched oxyalkylene monomer unit. The polymerizedpolyamine is preferably derived from the polyol through an aminationreaction.

The polymerized polyahl may be a homopolymer of a chiral diol or chiralcyclic ether, but is preferably a random, block, or grafted copolymerformed from the chiral diol or chiral cyclic ether and a second diol orcyclic ether. The chiral diol preferably has a formula (I) of:

where R₁ and R₄ are different linear or branched hydrocarbon moietieshaving 1 to about 10 carbon atoms, R₂ and R₃ are different moietiesselected from hydrogen or linear or branched hydrocarbon moieties having1 to about 10 carbon atoms. The chiral cyclic ether preferably has aformula (II) of:

where R₁ and R₄ are different linear or branched hydrocarbon moietieshaving 1 to about 10 carbon atoms, R₂ and R₃ are different moietiesselected from hydrogen or linear or branched hydrocarbon moieties having1 to about 10 carbon atoms. The second diol or cyclic ether preferablyhas 2 to about 20 carbon atoms, and may be chiral or achiral. Forexample, the chiral diol may be 2-methyl-1,4-butanediol; the chiralcyclic ether may be 2-methyl-tetrahydrofuran; the second diol may be1,4-butanediol; and the second cyclic ether may be tetrahydrofuran.

In one embodiment, the polymerized polyahl is a polyether polyahl havingat least one repeating branched oxyalkylene monomer unit, preferablyhaving a formula (III) of:

where Y₁ to Y₄ are independently hydrogen or hydrocarbon moieties and atleast one of which is an alkyl moiety having 1 to about 10 carbon atoms,and a, b and x are independently zero or integers from 1 to about 10 andat least one of which is greater than zero. The polymerized polyahl maybe a polyether polyol or polyether polyamine having a respective formula(IV) or (V) of:

where R₅ is a linear or branched hydrocarbon moiety comprising 2 toabout 20 carbon atoms, R₆ is a branched hydrocarbon moiety having 3 toabout 20 carbon atoms, m and n are independently zero or integers from 1to about 100, and z is an integer from 1 to about 100. Preferably, R₅may be —CH₂—CH₂—CH₂—CH₂—, R₆ is —CH₂—CH(CH₃)—CH₂—CH₂— or—CH₂—CH₂—CH(CH₃)—CH₂—, m and n are independently selected from about 5to about 50, and z is from 1 to about 50. The polymerized polyahl ismore preferably a substantially non-crystalline block co-polyetherpolyol or polyamine having a melting point of less than about 20° C.and, as it is used in the prepolymer, having a molecular weight of about500 to about 10,000.

The polymerized polyahl reacts with the isocyanate at an equivalentratio of about 0.01:1 to about 1:1, preferably forming a prepolymerhaving a NCO content of less than about 15 percent. The isocyanate maybe organic, modified organic, aliphatic, alicyclic, unsaturated,araliphatic, aromatic, substituted, or unsubstituted, comprisingisocyanate-containing monomers, dimers, trimers, multimeric adducts,oligomers, polymers, prepolymers, low-free-monomer prepolymers,quasi-prepolymers, diisocyanates, polyisocyanates, uretdiones,isocyanurates, or blends thereof. The prepolymer is then reacted with acuring agent at an equivalent ratio of about 1:0.6 to about 1:1.5. Thecuring agent includes saturated or unsaturated monomeric polyahls,oligomeric polyahls, polyether polyahls, polyester polyahls,polycaprolactone polyahls, polycarbonate polyahls, polyhydrocarbonpolyahls, polyamide polyahls, polyolefin polyahls, polyahls convertedfrom acid functional oligomers or polymers or ionomers thereof, diols,triols, tetraols, polyols, diamines, triamines, tetramines, polyamines,amine- and hydroxy-containing hybrid compounds, epoxies, andcombinations thereof. Preferably, the composition is substantiallysaturated. More preferably, all the components forming the compositionare substantially saturated.

Alternatively, the polyether polyahls or polymerized polyahls of thepresent invention, particularly those having a molecular weight of about200 to about 5,000, may be use as a curing agent to cure anypolyurethane or polyurea prepolymers, including those disclosed herein,at a prepolymer-to-curative equivalent ratio of about 1:0.6 to about1:1.5. They may be used alone or in combination or in combination withone or more of the curing agents disclosed herein, Preferably, thecomposition is substantially saturated. More preferably, all thecomponents forming the composition are substantially saturated.

The polyurethane or polyurea composition of the present inventioncomprising the polyether polyahl or the polymerized polyahl preferablyhas a material hardness of less than about 90 Shore D, more preferablyless than about 70 Shore D. The resulting golf ball preferably has acompression of less than about 100. Preferably, at least one of the golfball cover layers, such as an inner cover layer or an outer cover layer,is formed from a thermoplastic or thermoset polyurethane or polyureacomposition, and has a Shore D hardness of about 30 to about 70 and aflexural modulus of about 10,000 psi to about 80,000 psi. The golf ballmay further include one or more intermediate layers between the core andthe cover. At least one of these intermediate layers is preferablyformed from a thermoplastic material, such as ionomers, elastomers, oracid copolymers or terpolymers having an acid content of about 2% toabout 50% and being neutralized by 1 to about 100% or more.

The most preferred polymerized polyahls of the present invention arepoly(tetrahydrofuran-co-methyltetrahydrofuran) terminated with hydroxygroups and/or amine groups, having a preferred molecular weight of about1,000 to about 5,000. These co-polyether polyahls may be used in thecore, the intermediate layer, and/or the cover of a golf ball.

DEFINITIONS

As used herein, the term “polyahl” or “reactive polyahl” refers to anyone compound or a mixture of compounds containing a plurality of activehydrogen moieties per molecule. Illustrative of such active hydrogenmoieties are —OH (hydroxy group), —SH (thio group), —COOH (carboxylicacid group), and —NHR (amine group), with R being hydrogen, alkyl, aryl,or epoxy; all of which may be primary or secondary. These activehydrogen moieties are reactive to free isocyanate groups, formingurethane, urea, thiourea or corresponding linkage depending on theparticular active hydrogen moiety being reacted. The polyahls may bemonomers, homo-oligomers, co-oligomers, homopolymers, or copolymers, andinclude the compounds described in U.S. Pat. Nos. 4,394,491 and4,822,827. Oligomeric and polymeric polyahls having at least oneNCO-reactive group on each terminal of a backbone are typically employedas the soft segment in reaction products such as polyureas andpolyurethanes. Depending on the terminal groups, the oligomeric andpolymeric polyahls may be identified as polyols (with —OH terminalsonly), polyamines (with —NHR terminals only), or amino alcohol oligomersor polymers (with both —OH and —NHR terminals). Such polyahls with arelatively low molecular weight (less than about 5,000), and a widevariety of monomeric polyahls, are commonly used as curing agents. Thepolyahls are generally liquids or solids meltable at relatively lowtemperatures.

As used herein the term “chiral” is used on materials having a molecularstructure that is not superimposible on its mirror image. Some chiralmolecules have one or more chiral centers, in which an atom such ascarbon is bonded to four different moieties. Other chiral molecules maynot have any such chiral centers. Any one chiral molecule disclosedherein includes all of its stereoisomers and optical isomers, such as(R) and (S) enantiomers and diastereomers, and mixture thereof, such asracemic mixtures (i.e., exact 50:50 mixtures of opposite enantiomers).

As used herein, the term “saturated” or “substantially saturated” meansthat the compound or material of interest is fully saturated (i.e.,contains no double bonds, triple bonds, or aromatic ring structures), orthat the extent of unsaturation is negligible, e.g. as shown by abromine number in accordance with ASTM E234-98 of less than 10,preferably less than 5.

As used herein, the term “percent NCO” or “% NCO” refers to the percentby weight of free, reactive, and unreacted isocyanate functional groupsin an isocyanate-functional molecule or material. The total formulaweight of all the NCO groups in the molecule or material, divided by itstotal molecular weight, and multiplied by 100, equals the percent NCO.

As used herein, the term “equivalent” is defined as the number of molesof a functional group in a given quantity of material, and calculatedfrom material weight divided by equivalent weight, the later of whichrefers to molecular weight per functional group. For isocyanates theequivalent weight is (4210 grams)/% NCO; and for polyols, (56100grams)/OH#.

As used herein, the term “flexural modulus” or “modulus” refers to theratio of stress to strain within the elastic limit (measured in flexuralmode) of a material, indicates the bending stiffness of the material,and is similar to tensile modulus. Flexural modulus, typically reportedin Pascal (“Pa”) or pounds per square inch (“psi”), is derived inaccordance to ASTM D6272-02.

As used herein, the term “water vapor transmission rate” (“WVTR”) refersto the mass of water vapor that diffuses into a material of a giventhickness per unit area per unit time at a specific temperature andhumidity differential. Standard tests for WVTR include ASTM E96-00.

As used herein, the tern “material hardness” refers to indentationhardness of non-metallic materials in the form of a flat slab or buttonas measured with a durometer. The durometer has a spring-loaded indentorthat applies an indentation load to the slab, thus sensing its hardness.The material hardness can indirectly reflect upon other materialproperties, such as tensile modulus, resilience, plasticity, compressionresistance, and elasticity. Standard tests for material hardness includeASTM D2240-02b. Unless otherwise specified, material hardness reportedherein is in Shore D. Material hardness is distinct from the hardness ofa golf ball portion as measured directly on the golf ball (or otherspherical surface). The difference in value is primarily due to theconstruction, size, thickness, and material composition of the golf ballcomponents (i.e., center, core and/or layers) that underlie the portionof interest. One of ordinary skill in the art would understand that thematerial hardness and the hardness as measured on the ball are notcorrelated or convertible.

As used therein, the term “compression,” also known as “ATTIcompression” or “PGA compression,” refers to points derived from aCompression Tester (ATTI Engineering Company, Union City, N.J.), a scalewell known in the art for determining relative compression of aspherical object. Compression is a property of a material as measured ona golf ball construction (i.e., on-ball property), not a property of thematerial per se.

As used herein, the term “coefficient of restitution” or “COR” for golfballs is defined as the ratio of a ball's rebound velocity to itsinitial incoming velocity when the ball is fired out of an air cannoninto a rigid vertical plate. The faster a golf ball rebounds, the higherthe COR it has, the more the total energy it retains when struck with aclub, and the longer the ball flies. The initial velocity is about 50ft/s to about 200 ft/s, and is usually understood to be 125 ft/s, unlessotherwise specified. A golf ball may have different COR values atdifferent initial velocities.

The term “about,” as used herein in connection with one or more numbersor numerical ranges, should be understood to refer to all such numbers,including all numbers in a range.

DETAILED DESCRIPTION OF THE INVENTION

The cover of the golf ball provides the interface between the ball and aclub. Desirable properties for the cover include good moldability, highabrasion resistance, high tear strength, and high resilience. The covergenerally should provide sufficient strength for good performancecharacteristics and durability. The cover may have a single-layerconstruction, or a multi-layer construction that includes one or moreinner cover layers and an outer cover layer. The material compositionsdescribed herein, while applicable in any portion of the golf ball, arepreferably used to form cover layer(s), including single-layer covers,inner cover layers, and/or outer cover layers.

The cover layer, particularly the outer cover layer, of the presentinvention may comprise about 1 weight percent to about 100 weightpercent, preferably about 5 weight percent to about 95 weight percent,of a thermoplastic or thermoset composition. The composition, preferablyformed from a castable liquid reactive material, comprises apolymerization product of a chiral diol or chiral cyclic ether, or apolyether polyahl (polyol or polyamine) having a repeating branchedoxyalkylene monomer unit. In one embodiment, the composition comprises apolyurethane prepolymer of an isocyanate and a polyol. The polyol ispreferably the polymerization product having hydroxy terminals, or thepolyether polyol. The polyurethane prepolymer is typically cured with acuring agent to form a polyurethane composition suitable for golf ballcover applications.

The chiral diol suitable to form the polyol preferably has a formula (I)of:

where R₁ and R₄ are different linear or branched hydrocarbon, preferablyalkylene, moieties having 1 to about 10 carbon atoms, R₂ and R₃ aredifferent moieties selected from hydrogen or linear or branchedhydrocarbon, preferably alkyl, moieties having 1 to about 10 carbonatoms. More preferably, R₁ and R₄ are alkylene moieties having 1 toabout 6 carbon atoms, while at least one of R₂ and R₃ is an alkyl moietyhaving 1 to about 6 carbon atoms. The chiral cyclic ether suitable toform the polyol preferably has a formula (II) of:

where R₁ and R₄ are different linear or branched hydrocarbon, preferablyalkylene, moieties having 1 to about 10 carbon atoms, R₂ and R₃ aredifferent moieties selected from hydrogen or linear or branchedhydrocarbon, preferably alkyl, moieties having 1 to about 10 carbonatoms. More preferably, R₁ and R₄ are alkylene moieties having 1 toabout 6 carbon atoms, while at least one of R₂ and R₃ is an alkyl moietyhaving 1 to about 6 carbon atoms.

The chiral diol may self-polymerize through a condensation reaction, orco-polymerize with a second diol also via condensation, or polymerizewith a second cyclic ether through a base-catalyzed ring-openingreaction. The chiral cyclic ether may self-polymerize through anacid-catalyzed ring-opening reaction, or co-polymerize with a secondcyclic ether also via acid-catalyzed ring-opening, or polymerize with asecond diol through base-catalyzed ring opening. The second diol orcyclic ether may be chiral or achiral, which include the chiral diol(I), the chiral cyclic ether (II), and other alkylene diols, andpreferably have 2 to about 20 carbon atoms. In one embodiment, thesecond diol or cyclic ether has an alkylene moiety of 2 to about 12carbon atoms, preferably 3 to about 6 carbon atoms. The resulting polyolof the polymerization reaction may be a homopolymer of the chiral diolor chiral cyclic ether, but is preferably a random, block, or graftedcopolymer formed from the chiral diol or chiral cyclic ether and thesecond diol or cyclic ether. One of ordinary skill in the art wouldunderstand that the chiral diol (I) and the chiral cyclic ether may beconverted from one to the other using conventional chemistry. Likewise,the second diol and cyclic ether may also be inter-convertible.Conversion of the diols to the cyclic ethers may be particularlydesirable to enable subsequent ring-opening polymerization of the cyclicethers. The catalytic cyclization of diols into cyclic ethers is wellknown to the skilled in the art. As a non-limiting illustration, thechiral diol may be 2-methyl-1,4-butanediol; the chiral cyclic ether maybe 2-methyl-tetrahydrofuran; the second diol may be 1,4-butanediol(achiral); and the second cyclic ether may be tetrahydrofuran (achiral).Other chiral diols include 2,4-petanediol and 3-methyl-1,3-butanediol.

The polyol of the present invention has at least one repeating branchedoxyalkylene or alkylencoxy monomer unit, preferably a chiral oxyalkylenemonomer unit, having a formula (III) of:

where Y₁ to Y₄ are independently hydrogen or hydrocarbon, preferablyalkyl, moieties, at least one of which is an alkyl moiety having 1 toabout 10 carbon atoms, and a, b, and x are independently zero orintegers from 1 to about 10. Preferably, Y₁ to Y₄ all have less thanabout 6 carbon atoms, and a, b, and x are all less than about 6. Thepolyol may also have a second repeating oxyalkylene monomer unit whichis branched or, preferably, linear having 2 to about 20 carbon atoms.Exemplary linear and branched oxyalkylene monomer units include, but arenot limited to, —O—CH₂—CH(CH₃)—CH₂—CH₂—, —O—CH₂—CH₂—CH(CH₃)—CH₂—,—O—CH(CH₃)—CH₂—CH₂—CH₂—, —O—CH₂—CH₂—CH₂—CH(CH₃)—, —O—CH(CH₃)—CH₂—CH₂—,—O—CH₂—CH(CH₃)—CH₂—, —O—CH₂—CH₂—CH(CH₃)—, —O—C(CH₃)₂—CH₂—,—O—CH₂—C(CH₃)₂—, —O—CH(CH₂CH₃)—CH₂—, —O—CH₂—CH(CH₂CH₃)—,—O—CH(CH₃)—CH₂—, —O—CH₂—CH(CH₃)—, —O—CH₂—CH₂—CH₂—CH₂—CH₂—,—O—CH₂—CH₂—CH₂—CH₂—, —O—CH₂—CH₂—CH₂—, and —O—CH₂—CH₂—.

In a preferred embodiment, the polyol is a polyether polyol having aformula (IV) of:

where R₅ is a linear or branched hydrocarbon, preferably alkylene,moiety comprising 2 to about 20 carbon atoms, R₆ is a branchedhydrocarbon, preferably alkylene, moiety having 3 to about 20 carbonatoms, m and n are independently zero or integers from 1 to about 100,and z is an integer from 1 to about 100. R₆ may be essentiallyequivalent to the structure of R₁—C(R₂)(R₃)—R₄ in the formulas (I) and(II) above, or —O—R₆ may be essentially equivalent to the branchedoxyalkylene monomer unit (III). The polyether polyol (IV) can be formedfrom the chiral diol (I) or chiral ether (II) and the second diol orcyclic ether at a molar ratio of about 85:15 to about 20:80. Thesynthesis of polyether polyols from chiral cyclic ethers and achiralcyclic ethers is disclosed in U.S. Pat. Nos. 3,358,042, 4,120,850,4,590,285, and 4,960,849, the disclosures of which are incorporatedherein by reference in their entirety.

Preferably, the polyether polyol is formed from a ring-openingco-polymerization of 2-methyl-tetrahydrofuran with tetrahydrofuran, sothat R₆ is either —CH₂—CH(CH₃)—CH₂—CH₂— or —CH₂—CH₂—CH(CH₃)—CH₂—, R₅ is—CH₂—CH₂—CH₂—CH₂—, m and n are independently selected from about 5 toabout 50, and z is from 1 to about 50. This polyether polyol is referredto as a modified polytetramethylene ether glycol (“PTMEG”), or ahydroxy-terminated poly(tetrahydrofuran-co-methyltetrahydrofuran) ether.

The polyol as described above may be converted into a polyamine, i.e.,replacing the terminal hydroxy groups with amine groups, through anamination reaction as understood by the skilled in the art. Theresulting polyamine may then be reacted with an isocyanate to form apolyurea prepolymer, suitable for a polyurea composition in golf ballapplications. In particular, the polyether polyol (IV) may be aminatedto a polyamine having a formula (V) of:

where R₅ is a linear or branched hydrocarbon, preferably alkylene,moiety comprising 2 to about 20 carbon atoms, R₆ is a branchedhydrocarbon, preferably alkylene, moiety having 3 to about 20 carbonatoms, m and n are independently zero or integers from 1 to about 100,and z is an integer from 1 to about 100.

The polyahls of the present invention, including the polyols and thepolyamines derived therefrom as described above, may further comprisesubstituted groups or moieties. Suitable substitution groups or moietiesinclude, without limitation, fluoride, chloride, bromide, iodide,cyanide, sulfide, silicone, carboxylate, sulfonate, phosphonate,acrylate, methacrylate, epoxy, hydrocarbon, fluorocarbon, halogenatedpolyether, polyalkylene oxide, aromatic, or vinyl groups or moieties;urethane or urea units; terminal or pendant functional groups ormoieties, such as primary or secondary hydroxyl groups, primary orsecondary amine groups, isocyanate groups, (meth)acrylate groups, epoxygroups, neutralized or un-neutralized acid groups, or ethylenicallyunsaturated polymerizable groups. These units, groups, moieties, orcombinations thereof may be present in the polyahls to provide enhancedfunctionality and/or reactivity.

The unique structural and compositional characteristics of the polyahlsresults in their physical, chemical, thermal, and other properties thatare desirable and advantageous in golf ball applications. For example,these polyahls have lowered crystallinity, lowered melting points,liquid property at a widened range of temperature, improved flexibilityat low temperatures, reduced energy loss in tensile mode, improved flexfatigue, improved resilience, and other enhanced elastic properties. Thepolyahls of the present invention preferably has at least one ofmaterial hardness, flexural modulus, elastic modulus, storage modulus,elongation, tensile strength, tear strength, and compression thatfluctuates less than about 10% in a temperature range of about −20° C.to about 20° C., more preferably about −25° C. to about 50° C., and mostpreferably about −30° C. to about 100° C. Suitable polyahls have amolecular weight of at least about 200, a polydispersity of less thanabout 3, a melting point of less than about 15° C., a flash point of atleast about 250° C., a viscosity of about 50 cps to about 20,000 cps at40° C., a density of about 0.8 g/cm³ to about 1.2 g/cm³, a materialhardness of less than about 90 Shore D, a percent rebound of at leastabout 40%, a hysteresis of less than about 50%, a flexural or elasticmodulus of at least about 500 psi, and a water vapor transmission rateof less than about 2 g/(m²×day). The molecular weight of the preferredpolyahls is preferably about 500 to about 10,000, more preferably about1,000 to about 5,000. The melting point of the preferred polyahls ispreferably about 15° C., and more preferably less than about 12° C. Asunderstood to one skilled in the art, melting point of an organicmaterial such as the polyahls of the present invention are also referredto as freezing point. The polydispersity of the preferred polyahls ispreferably less than about 2.5, and more preferably less than about 2.1.The polyahls further have a hydroxyl number or amine number of about 10to about 300, preferably about 20 to about 150.

The polyahl of the present invention, alone or in a blend, may bereacted with an isocyanate at an equivalent ratio of about 0.01:1 toabout 1:1 to form a polyurethane prepolymer or polyurea prepolymerhaving a NCO content of less than about 30 percent, preferably less thanabout 15 percent. Any isocyanate available to one of ordinary skill inthe art is suitable for use according to the invention. The isocyanatemay be organic, modified organic, saturated, aliphatic, alicyclic,unsaturated, araliphatic, aromatic, substituted, or unsubstituteddiisocyanate or polyisocyanate monomers having two or more free reactiveisocyanate (“NCO”) groups; isomers thereof; modified derivativesthereof; dimers thereof; trimers thereof; or isocyanurates thereof. Theisocyanate may also include any isocyanate-terminated multimericadducts, oligomers, polymers, prepolymers, low-free-monomer prepolymers,quasi-prepolymers, and modified polyisocyanates derived from theisocyanates and polyisocyanates above. Low-free-monomer prepolymersrefer to prepolymers having free isocyanate monomer levels less thanabout 0.5 weight percent.

In addition to the free reactive isocyanate groups, the suitableisocyanate further comprises at least one cyclic, aromatic, aliphatic,linear, branched, or substituted hydrocarbon moiety R containing from 1to about 20 carbon atoms, such as arylenes, aralkylenes, alkylenes, orcycloalkylenes. When multiple cyclic or aromatic groups are present,linear, branched or substituted hydrocarbons containing from 1 to about10 carbon atoms can be present as spacers between such cyclic oraromatic groups. In some cases, the cyclic or aromatic group(s) may besubstituted at the 2-(ortho-), 3-(meta-), and/or 4-(para-) positions.Substituted groups may include, but are not limited to, halogens, cyanogroups, amine groups, silyl groups, hydroxyl groups, acid groups, alkoxygroups, primary or secondary or tertiary hydrocarbon groups, or acombination of two or more groups thereof. Any and all of theisocyanates disclosed herein may be used alone or in combination of twoor more thereof.

Preferred isocyanates include diisocyanates (having two NCO groups permolecule), dimerized uretdiones thereof, trimerized isocyanuratesthereof, and polyisocyanates such as monomeric triisocyanates.Diisocyanates typically have the generic structure of OCN—R—NCO.Exemplary diisocyanates include, but are not limited to, unsaturatedisocyanates such as: p-phenylene diisocyanate (“PPDI,” i.e.,1,4-phenylene diisocyanate), m-phenylene diisocyanate (“MPDI,” i.e.,1,3-phenylene diisocyanate), o-phenylene diisocyanate (i.e.,1,2-phenylene diisocyanate), 4-chloro-1,3-phenylene diisocyanate,toluene diisocyanate (“TDI”), m-tetramethylxylene diisocyanate(“m-TMXDI”), p-tetramethylxylene diisocyanate (“p-TMXDI”), 1,2-, 1,3-,and 1,4-xylene diisocyanates, 2,2′-, 2,4′-, and 4,4′-biphenylenediisocyanates, 3,3′-dimethyl-4,4′-biphenylene diisocyanate (“TODI”),2,2′-, 2,4′-, and 4,4′-diphenylmethane diisocyanates (“MDI”),3,3′-dimethyl-4,4′-diphenylmethane diisocyanate, carbodiimide-modifiedMDI, polyphenylene polymethylene polyisocyanate (“PMDI,” i.e. polymericMDI), 1,5-naphthalene diisocyanate (“NDI”), 1,5-tetrahydronaphththalenediisocyanate, anthracene diisocyanate, tetracene diisocyanate; andsaturated isocyanates such as: 1,4-tetramethylene diisocyanate,1,5-pentamethylene diisocyanate, 2-methyl-1,5-pentamethylenediisocyanate, 1,6-hexamethylene diisocyanate (“HDI”) and isomersthereof, 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanates,1,7-heptamethylene diisocyanate and isomers thereof, 1,8-octamethylenediisocyanate and isomers thereof, 1,9-novamethylene diisocyanate andisomers thereof, 1,10-decamethylene diisocyanate and isomers thereof,1,12-dodecane diisocyanate and isomer thereof, 1,3-cyclobutanediisocyanate, 1,2-, 1,3-, and 1,4-cyclohexane diisocyanates, 2,4- and2,6-methylcyclohexane diisocyanates (“HTDI”), isophorone diisocyanate(“IPDI”), isocyanatomethylcyclohexane isocyanate,isocyanatoethylcyclohexane isocyanate, bis(isocyanatomethyl)cyclohexane(i.e., 1,4-cyclohexane-bis(methylene isocyanate)),4,4′-dicyclohexylmethane diisocyanate (“H₁₂MDI,” i.e.,bis(4-isocyanatocyclohexyl)-methane), 2,4′- and 4,4′-dicyclohexanediisocyanates, 2,4′- and 4,4′-bis(isocyanatomethyl) dicyclohexanes.Dimerized uretdiones of diisocyanates and polyisocyanates include, forexample, unsaturated isocyanates such as uretdiones of toluenediisocyanates, uretdiones of diphenylmethane diisocyanates; andsaturated isocyanates such as uretdiones of hexamethylene diisocyanates.Trimerized isocyanurates of diisocyanates and polyisocyanates include,for example, unsaturated isocyanates such as trimers of diphenylmethanediisocyanate, trimers of tetramethylxylene diisocyanate, isocyanuratesof toluene diisocyanates; and saturated isocyanates such asisocyanurates of isophorone diisocyanate, isocyanurates of hexamethylenediisocyanate, isocyanurates of trimethyl-hexamethylene diisocyanates.Monomeric triisocyanates include, for example, unsaturated isocyanatessuch as 2,4,4′-diphenylene triisocyanate, 2,4,4′-diphenylmethanetriisocyanate, 4,4′,4″-triphenylmethane triisocyanate; and saturatedisocyanates such as 1,3,5-cyclohexane triisocyanate.

Among the above-listed isocyanates, all of the saturated isocyanatesdisplay satisfactory light stability when used in golf balls coverlayers, and are most preferred in golf ball outer cover layer or coatingcompositions. Other relatively light-stable isocyanates include some ofthe unsaturated isocyanates, particularly those that are araliphatic,including 1,2-, 1,3-, and 1,4-xylene diisocyanates, m-tetramethylxylenediisocyanate, p-tetramethylxylene diisocyanate, uretdiones of toluenediisocyanates, isocyanurates of toluene diisocyanates, and isocyanuratesof diphenylmethane diisocyanates.

Isocyanate-terminated oligomers or polymers include any oligomers,polymers, prepolymers, or quasi-prepolymers having at least two freereactive isocyanate groups as terminal groups, and optionally morependant isocyanate groups, on the oligomeric or polymeric backbones.Isocyanate-terminated prepolymers and quasi-prepolymers are well knownto the skilled artisan, and include, but are not limited to, thereaction products of any one or combination of two or more of theisocyanates listed above and any one or combination of two or more ofthe polyahls disclosed herein below. It is well understood in the artthat material hardness of polyureas, polyurethanes, andpolyurethane/polyurea hybrids may be modified by adjusting the percentNCO content in the isocyanate-terminated prepolymer. Conventionally, theisocyanate-terminated prepolymer has less than about 30% NCO, preferablyno greater than about 15% NCO. A percent NCO of about 4% to about 9% mayprovide a relatively soft elastomer (polyurethane, polyurea, or hybridthereof) preferably suitable for use in golf ball covers or outer coverlayers. A percent NCO of about 7% to about 15% may provide a relativelyhard elastomer preferably suitable for use in golf ball intermediatelayers, outer core layer, and/or inner cover layers.

The above-described polyahls, present by about 1 weight percent to about100 weight percent in a blend, may be blended with one or more polyahlsknown to one of ordinary skill in the art to form the polyurethaneprepolymers or polyurea prepolymers. Suitable polyahls for the blend maybe organic, modified organic, saturated, aliphatic, alicyclic,unsaturated, araliphatic, aromatic, substituted, or unsubstituted. Thepolyahl preferably has two or more reactive hydrogen groups permolecule, such as primary or secondary hydroxy groups or amine groups,and at least one cyclic, aromatic, aliphatic, linear, branched, orsubstituted hydrocarbon moiety containing from 1 to about 20 carbonatoms, such as arylenes, aralkylenes, alkylenes, or cycloalkylenes. Whenmultiple cyclic or aromatic groups are present, linear, branched orsubstituted hydrocarbons containing from 1 to about 10 carbon atoms canbe present as spacers between such cyclic or aromatic groups. In somecases, the cyclic or aromatic group(s) may be substituted at the2-(ortho-), 3-(meta-), and/or 4-(para-) positions. Substituted groupsmay include, but are not limited to, halogens, cyano groups, aminegroups, silyl groups, hydroxyl groups, acid groups, alkoxy groups,primary or secondary or tertiary hydrocarbon groups, or a combination oftwo or more groups thereof. The isocyanate-reactive hydroxy and/or aminegroups may be terminal or pendant groups on the oligomeric or polymericbackbone, and in the case of secondary amine groups, may even beembedded within the backbone. Any and all of the polyahls disclosedherein may be used alone or in combination of two or more thereof.

Suitable polyols have a molecular weight of at least about 200 and atleast two primary or secondary hydroxyl terminal groups per molecule,and include, but are not limited to: polyether polyols such as PTMEG,modified PTMEG, poly(oxyethylene) glycol, poly(oxypropylene) glycol,poly(oxyethylene-oxypropylene) glycol, (ethylene oxide)-cappedpoly(oxypropylene) ether glycol; polyester polyols such as poly(ethyleneadipate) glycol, poly(butylene adipate) glycol, poly(hexamethyleneadipate) glycol, poly(ethylene propylene adipate) glycol, poly(ethylenebutylene adipate) glycol, poly(hexamethylene butylene adipate) glycol,(o-phthalate-1,6-hexanediol)-based polyester polyol, poly(ethyleneterephthalate)-based polyester polyol; polycaprolactone polyols such as(alkylene oxide)-initiated polycaprolactones, (ethyleneglycol)-initiated polycaprolactone, (diethylene glycol)-initiatedpolycaprolactone, (propylene glycol)-initiated polycaprolactone,(dipropylene glycol)-initiated polycaprolactone,1,4-butanediol-initiated polycaprolactone, trimethylolpropane-initiatedpolycaprolactone, (neopentyl glycol)-initiated polycaprolactone,1,6-hexanediol-initiated polycaprolactone, PTMEG-initiatedpolycaprolactone; polycarbonate polyols such as poly(phthalatecarbonate) glycol, poly(hexamethylene carbonate) glycol, (bisphenolA)-based polycarbonate glycols; polyhydrocarbon polyols such aspolyisoprene polyol, poly(hydrogenated isoprene) polyol,hydroxy-terminated liquid isoprene rubber, polybutadiene polyol,poly(hydrogenated butadiene) polyol (like Polytail H and Polytail HAfrom Mitsubishi Kasei Corp.), poly(ethylene-co-propylene) polyol,poly(ethylene-co-butylene) polyol, poly(alkylene-co-styrene) polyol,Kraton® polyols, glycerol-based polyols, (castor oil)-based polyols;polyols converted from acid functional oligomers or polymers (orionomers thereof derived from partial or full neutralization withorganic or inorganic cations), such as dimerate or trimerate polyols offatty acids or isostearic acid; and other polyols such as polyolefinpolyols and polyamide polyols.

Saturated members of the above-listed polyols (aliphatic, alicyclic, orfully hydrogenated) are preferred for use in the present invention,because they afford superior light stability when incorporated into thegolf ball cover composition. Exemplary saturated polyols include, butare not limited to, PTMEG, modified PTMEG, poly(oxyethylene) glycol,poly(oxypropylene) glycol, poly(oxyethylene-oxypropylene) glycol,(ethylene oxide)-capped poly(oxypropylene) ether glycol, poly(ethyleneadipate) glycol, poly(butylene adipate) glycol, poly(hexamethyleneadipate) glycol, poly(ethylene propylene adipate) glycol, poly(ethylenebutylene adipate) glycol, poly(hexamethylene butylene adipate) glycol,(alkylene oxide)-initiated polycaprolactones, (ethyleneglycol)-initiated polycaprolactone, (diethylene glycol)-initiatedpolycaprolactone, (propylene glycol)-initiated polycaprolactone,(dipropylene glycol)-initiated polycaprolactone,1,4-butanediol-initiated polycaprolactone, trimethylolpropane-initiatedpolycaprolactone, (neopentyl glycol)-initiated polycaprolactone,1,6-hexanediol-initiated polycaprolactone, PTMEG-initiatedpolycaprolactone, poly(hexamethylene carbonate) glycol, saturatedpoly(hydrogenated isoprene) polyol, saturated poly(hydrogenatedbutadiene) polyol, poly(ethylene-co-propylene) polyol,poly(ethylene-co-butylene) polyol, poly(alkylene-co-styrene) polyol,Kraton® polyols, saturated dimerate or trimerate polyols of fatty acidsor isostearic acid, saturated polyolefin polyols, saturated polyamidepolyols, saturated glycerol-based polyols, and saturated (castoroil)-based polyols.

Suitable polyamines preferably have a molecular weight of at least about200 and at least two primary or secondary amine terminal groups permolecule. Because lower molecular weight amine-terminated polymers maybe prone to forming solids, a high molecular weight of at least about1,000 is more preferred. Exemplary polyamines include, but are notlimited to: polyether polyamines such as polyoxyalkylene diamines,polyoxyethylene diamines, polyoxypropylene diamines,poly(oxyethylene-oxypropylene) diamines, polyoxypropylene triamine,poly(tetramethylene ether) diamines, (ethylene oxide)-cappedpolyoxypropylene ether diamines, poly(triethyleneglycol) diamines,poly(trimethylolpropane) triamines,polyethyleneglycol-di(p-aminobenzoate),polytetramethyleneoxide-di(p-aminobenzoate), glycerin-based triamines;and other polyamines such as polyester polyamines, polycaprolactonepolyamines, polycarbonate polyamines, polyhydrocarbon polyamines,polyamines converted from acid functional oligomers or polymers orionomers thereof, polyolefin polyamines, and polyamide polyamines. Anyof these polyamines may be prepared from the above-listed polyolsthrough reductive amination of polyether polyols with ammonia andhydrogen in the presence of a catalyst, hydrogenation of cyanoethylatedpolyols, amination of polyol/sulfonic acid esters, reacting polyols withepichlorohydrin and a primary amine, or any other methods known to theskilled artisan.

Exemplary polyamines converted from the polyols above include, withoutlimitation, polytetramethylene ether diamine, modifiedpolytetramethylene ether diamine,poly(tetrahydrofuran-co-methyltetrahydrofuran) ether diamine,poly(oxyethylene) diamine, poly(oxypropylene) ether diamine or triamine,poly(oxyethylene-oxypropylene) diamine, (ethylene oxide)-cappedpoly(oxypropylene) diamine, poly(ethylene adipate) diamine,poly(butylene adipate) diamine, poly(hexamethylene adipate) diamine,poly(ethylene propylene adipate) diamine, poly(ethylene butyleneadipate) diamine, poly(hexamethylene butylene adipate) diamine,(o-phthalate-1,6-hexanediol)-based polyester polyamine, poly(ethyleneterephthalate)-based polyester polyamine, (alkylene oxide)-initiatedpolycaprolactone polyamine, (ethylene glycol)-initiated polycaprolactonepolyamine, (diethylene glycol)-initiated polycaprolactone polyamine,(propylene glycol)-initiated polycaprolactone polyamine, (dipropyleneglycol)-initiated polycaprolactone polyamine, 1,4-butanediol-initiatedpolycaprolactone polyamine, trimethylolpropane-initiatedpolycaprolactone polyamine, (neopentyl glycol)-initiatedpolycaprolactone polyamine, 1,6-hexanediol-initiated polycaprolactonepolyamine, (polytetramethylene ether glycol)-initiated polycaprolactonepolyamine, poly(phthalate carbonate) diamine, poly(hexamethylenecarbonate) diamine, (bisphenol A)-based polycarbonate diamines,polyisoprene polyamine, poly(hydrogenated isoprene) polyamine,amine-terminated liquid isoprene rubber, polybutadiene polyamine,poly(hydrogenated butadiene) polyamine, poly(ethylene-co-propylene)polyamine, poly(ethylene-co-butylene) polyamine,poly(alkylene-co-styrene) polyamine, glycerol-based polyamines, (castoroil)-based polyamines, dimerate or trimerate polyamines of fatty acidsor isostearic acid, or acid functional polyamines. Saturated (aliphatic,alicyclic, or fully hydrogenated) polyamines are preferred for use ingolf balls to provide superior light stability, and includepolyoxyalkylene diamines, polyoxyethylene diamines, polyoxypropylenediamines, poly(oxyethylene-oxypropylene) diamines, polyoxypropylenetriamines, poly(tetramethylene ether) diamines, (ethylene oxide)-cappedpolyoxypropylene ether diamines, poly(triethyleneglycol) diamines,poly(trimethylolpropane) triamines, saturated glycerin-based triamines,saturated polyester polyamines, saturated polycaprolactone polyamines,saturated polycarbonate polyamines, saturated polyhydrocarbonpolyamines, saturated acid functional polyamines, saturated polyolefinpolyamines, and saturated polyamide polyamines.

The above-listed polyahls, particularly those having a molecular weightof less than about 10,000, preferably less than about 5,000, mayoptionally be used as curing agents for chain-extension and/or crosslinkin a polyurethane or polyurea composition. In particular, the curingagents react with polyurethane prepolymers or polyurea prepolymers,including the ones discussed above, to afford the desired golf ballcompositions. Other suitable curing agents for the invention includepolyahls and epoxies, preferably hydroxy curatives, amine curatives, andamino alcohol curatives. Suitable hydroxy curatives have a molecularweight of about 50 to about 5,000, and include, but are not limited to,unsaturated diols such as 1,3-bis(2-hydroxyethoxy) benzene,1,3-bis[2-(2-hydroxyethoxy)ethoxy] benzene,N,N-bis(β-hydroxypropyl)aniline,1,3-bis{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy} benzene,hydroquinone-di(β-hydroxyethyl)ether,resorcinol-di(β-hydroxyethyl)ether; saturated diols such as ethyleneglycol, diethylene glycol, polyethylene glycol, propylene glycol,dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol,1,2-, 1,3-, 1,4-, or 2,3-butanediols, 2-methyl-1,4-butanediol,2,3-dimethyl-2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol,dimethylolcyclohexane, 1,3-bis(2-hydroxyethoxy)cyclohexane,1,3-bis[2-(2-hydroxyethoxy)ethoxy]cyclohexane,1,3-bis{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}cyclohexane; unsaturatedtriols such as castor oil (i.e., triricinoleoyl glycerol); saturatedtriols such as 1,2,4-butanetriol, 1,2,6-hexanetriol, trimethylolethane(i.e., 1,1,1-tri(hydroxymethyl)ethane), trimethylolpropane (i.e.,2,2-di(hydroxymethyl)-1-butanol), triethanolamine, triisopropanolamine;unsaturated tetraols such as2,4,6-tris(N-methyl-N-hydroxymethyl-aminomethyl)phenol; saturatedtetraols such as pentaerythritol (i.e., tetramethylolmethane),tetrahydroxypropylene ethylenediamine (i.e.,N,N,N′,N′-tetrakis(2-hydroxypropyl)-ethylenediamine); and othermonomeric polyols such as mannitol (i.e., 1,2,3,4,5,6-hexanehexol) andsorbitol (an enantiomer of mannitol) (both saturated).

Suitable amine curatives have a molecular weight of about 50 to about5,000, and include, but are not limited to, unsaturated diamines such asm-phenylenediamine, p-phenylenediamine, 1,2- or1,4-bis(sec-butylamino)-benzene, 3,5-diethyl-(2,4 or2,6)-toluenediamine, 3,5-dimethylthio-(2,4 or 2,6)-toluenediamine,3,5-diethylthio-(2,4 or 2,6)-toluenediamine,4,4′-diamino-diphenylmethane (i.e., 4,4′-methylene-dianiline or “MDA”),3,3′-dimethyl-4,4′-diamino-diphenylmethane,3,3′-diethyl-5,5′-dimethyl-4,4′-diamino-diphenylmethane (i.e.,4,4′-methylene-bis(2-ethyl-6-methyl-benezeneamine)),3,3′-dichloro-4,4′-diamino-diphenylmethane (i.e.,4,4′-methylene-bis(2-chloroaniline) or “MOCA”),3,3′-diethyl-5,5′-dichloro-4,4′-diamino-diphenylmethane,3,3′,5,5′-tetraethyl-4,4′-diamino-diphenylmethane (i.e.,4,4′-methylene-bis(2,6-diethylaniline) or “MDEA”),2,2′-dichloro-3,3′,5,5′-tetraethyl-4,4′-diamino-diphenylmethane (i.e.,4,4′-methylene-bis(3-chloro-2,6-diethyleneaniline) or “MCDEA”),3,3′-dichloro-4,4′-diamino-diphenylmethane,4,4′-methylene-bis(2,3-dichloroaniline) (i.e.,2,2′,3,3′-tetrachloro-4,4′-diamino-diphenylmethane or “MDCA”),4,4′-bis(sec-butylamino)-diphenylmethane,N,N′-dialkylamino-diphenylmethane,trimethyleneglycol-di(p-aminobenzoate),polyethyleneglycol-di(p-aminobenzoate),polytetramethyleneglycol-di(p-aminobenzoate); saturated diamines such asethylene diamine, 1,3-propylene diamine, 2-methyl-pentamethylenediamine, hexamethylene diamine, 2,2,4- and 2,4,4-trimethyl-1,6-hexanediamine, imino-bis(propylamine), imido-bis(propylamine),methylimino-bis(propylamine) (i.e.,N-(3-aminopropyl)-N-methyl-1,3-propanediamine),1,4-bis(3-aminopropoxy)butane (i.e.,3,3′-[1,4-butanediylbis-(oxy)bis]-1-propanamine),diethyleneglycol-bis(propylamine) (i.e.,diethyleneglycol-di(aminopropyl)ether),4,7,10-trioxatridecane-1,13-diamine, polyoxyethylene diamines,polyoxypropylene diamines, poly(oxyethylene-oxypropylene) diamines,(ethylene oxide)-capped polyoxypropylene ether diamines,polytetramethylene ether diamines, 1-methyl-2,6-diamino-cyclohexane,1,4-diamino-cyclohexane, 1,3- or 1,4-bis(methylamino)-cyclohexane,isophorone diamine, 1,2- or 1,4-bis(sec-butylamino)-cyclohexane,N,N′-diisopropyl-isophorone diamine, 4,4′-diamino-dicyclohexylmethane,3,3′-dimethyl-4,4′-diamino-dicyclohexylmethane,3,3′-dichloro-4,4′-diamino-dicyclohexylmethane,N,N′-dialkylamino-dicyclohexylmethane,3,3′-diethyl-5,5′-dimethyl-4,4′-diamino-dicyclohexylmethane,3,3′-diethyl-5,5′-dichloro-4,4′-diamino-dicyclohexylmethane,3,3′,5,5′-tetraethyl-4,4′-diamino-dicyclohexylmethane (i.e.,4,4′-methylene-bis(2,6-diethylaminocyclohexane)),2,2′-dichloro-3,3′,5,5′-tetraethyl-4,4′-diamino-dicyclohexylmethane,3,3′-dichloro-4,4′-diamino-dicyclohexylmethane,3,3′-dichloro-2,2′,6,6′-tetraethyl-4,4′-diamino-dicyclohexylmethane,2,2′,3,3′-tetrachloro-4,4′-diamino-dicyclohexylmethane,4,4′-bis(sec-butylamino)-dicyclohexylmethane; triamines such asdiethylene triamine, dipropylene triamine, (propylene oxide)-basedtriamines (i.e., polyoxypropylene triamines), trimethylolpropane-basedtriamines, glycerin-based triamines,N-(2-aminoethyl)-1,3-propylenediamine (i.e., N₃-amine) (all saturated);tetramines such as triethylene tetramine,N,N′-bis(3-aminopropyl)ethylenediamine (i.e., N₄-amine) (bothsaturated); and other polyamines such as tetraethylene pentamine (alsosaturated).

Suitable amino alcohol curatives may be monomeric, oligomeric, orpolymeric, having at least one free reactive hydroxy group and at leastone free reactive amine group. The hydroxy and amine groups may beterminal or pendant groups on the oligomeric or polymeric backbone, andin the case of secondary amine groups, may even be embedded within thebackbone. Non-limiting examples of monomeric amino alcohol curativesinclude monoethanolamine (saturated), monoisopropanolamine (saturated),diethanolamine (saturated), diisopropanolamine (saturated), and2-propanol-1,1′-phenylaminobis (unsaturated).

For best light stability, all reactants in the polyurethane or polyureacompositions are preferably saturated, including the curing agents, thepolyahls, and the isocyanates. Most preferred saturated curatives are4,4′-bis-(sec-butylamino)-dicyclohexylmethane,2,3-dimethyl-2,3-butanediol, 2-methyl-1,3-propanediol,2-methyl-1,4-butanediol, 1,4-butanediol, and 1,4-cyclohexyldimethylol.In one embodiment, a hindered secondary diamine having a high level ofstearic hindrance, such as 4,4′-bis(sec-butylamino)-dicyclohexylmethane(Clearlink® 1000), N,N′-di(ethylmaleate-amino)-dicyclohexylmethane(i.e., 4,4′-bis(diethylsuccinato-amino)-dicyclohexylmethane, Desmophen®NH 1420), N,N′-di(ethylmaleate-amino)-dimethyl-dicyclohexylmethane(i.e.,3,3′-dimethyl-4,4′-bis(diethylsuccinato-amino)-dicyclohexylmethane,Desmophen® NH 1520), N,N′-diethylmaleate-2-methyl-pentamethylene diamine(Desmophen® NH 1220), or N,N′-diisopropyl-isophorone diamine, may beused alone or in combination of other curing agent(s) to beneficiallyslow down the curing process. Clearlink® curatives are available fromUOP LLC of Des Plaines, Ill., and Desmophen® NH polyaspartic esters areavailable from Bayer Corporation of Pittsburgh, Pa. Other secondarydiamines and polyamines are disclosed in U.S. Pat. Nos. 5,236,741 and5,126,170, which are incorporated by reference in their entirety. Inanother embodiment, a curing agent having a relatively low freezingpoint may be used as a freezing point depressant. Such dual functionalcuring agents include, without limitation, 2-methyl-1,3-propanediol and2-methyl-1,4-butanediol. Other useful freezing point depressants aredisclosed in co-pending U.S. patent application Ser. No. 10/339,603,which is incorporated herein by reference in its entirety.

As described above, the polyahls formed at least from the chiral diol orchiral ether of the present invention, particularly the polyetherpolyahls, may be incorporated into a prepolymer, used as a curing agent,or both, in the elastomeric reaction product that forms the golf ballcover layer. In particular, the polyahls are incorporated into one ormore soft segments of the reaction product, and are substantially absentin any hard segments of the reaction product. To form the prepolymer,the polyahl, alone or in a blend with other polyahls disclosed herein,may react with one or more isocyanates at an equivalent ratio of about0.01:1 to about 1:1. When the polyether polyahl is used alone, theequivalent ratio is preferably about 0.3:1 to about 0.6:1, morepreferably about 0.5:1. The weight ratio of the polyether polyahl to anyother polyahl(s) in a blend may be about 1:20 to about 20:1. The polyahlused in the prepolymer may have a relatively high molecular weight,preferably at least about bout 500, more preferably from about 500 toabout 10,000, and most preferably from about 1,000 to about 5,000. Theresulting prepolymer may be a polyurethane prepolymer, a polyureaprepolymer, or a polyurethane/polyurea prepolymer. The above-listedcuring agents, used alone or in combination of two or more thereof, maythen be used to cure the prepolymer into a thermoplastic or thermosetpolyurethane, polyurea, or polyurea/polyurethane hybrid. An equivalentratio of the prepolymer to the curing agent is preferably about 1:0.6 toabout 1:1.5, more preferably about 1:0.8 to about 1:1.2, and mostpreferably about 1:0.95.

When used as a curing agent, the polyahl may have a molecular weightrelative lower than those suitable in the prepolymer, preferably lessthan about 10,000, more preferably about 200 to about 5,000, and mostpreferably about 500 to about 3,000. The polyahl curative may be usedalone or in combination with other curatives disclosed above.Preferably, the polyahl constitutes at least about 1 weight percent ofthe total curative mixture, more preferably about 5 weight percent toabout 100 weight percent. The polyahl curative alone or in a blend maybe used to react with any prepolymers at an equivalent ratio of 0.6:1 toabout 1.5 to 1. The prepolymers include those disclosed herein, such asthe polyether polyahl-based prepolymers, and any prepolymers formed fromany combinations of the polyahls and the isocyanates listed above. Suchprepolymers may have only urethane bonds (polyurethane prepolymers),only urea bonds (polyurea prepolymer), or both (polyurethane/polyureahybrid prepolymer). Preferably, the prepolymer and the reactantstherein, the polyahl curative, and any other optional curatives are allsaturated.

A variety of additives can optionally be incorporated into the coverlayer compositions of the present invention. For example, a catalyst maybe employed to promote the reaction between the curing agent and theprepolymer. Suitable catalysts include, but are not limited to, zinccatalysts such as zinc octoate; cobalt (II) octoate, bismuth catalysts;tin catalysts, such as dibutyltin dilaurate (Dabco® T-12), dibutyltindiacetate (Dabco® T-1), dibutyltin maleate, tin (II) ethylhexoate, tin(II) laurate, tin (II) octoate, tin (II) chloride, tin (IV) chloride,dibutyltin dimethoxide (Fascat® 4211), dibutyltin dibutoxide (Fascat®4214), dimethyl-bis[(1-oxoneodecyl)oxy] stannane (Formez® UL-28),di(n-octyl)tin bis(isooctyl-mercaptoacetate) (Formez® UL-29),1,3-diacetoxytetrabutyl-stannoxane, and 2-ethylhexyl-titanate; aminecatalysts, such as triethylenediamine (Dabco® 33-LV), triethylamine,tributylamine, or N-methyl-morpholine; organic acids, such as aceticacid, adipic acid, azelaic acid, octanoic acid, or oleic acid; delayedheated-activated catalysts, such as phenol-blocked1,8-diaza-bicyclo(5,4,0)undecene-7 (Polycat™ SA-1/10), Polycat™ SA-102,or Polycat™ 8154.

These catalysts may be used alone or in combination of two or morethereof, and are added in an amount sufficient to catalyze thepolymerization reaction, preferably about 0.001 weight percent to about5 weight percent based on the total weight of the formulation, morepreferably about 0.005 weight percent to about 3 weight percent.Unconventionally high levels of catalysts allow lowered processingtemperature and mixing speed while retain comparable cure. The tincatalyst amount used is preferably about 0.05 weight percent to about 1weight percent, more preferably about 0.25 weight percent to about 0.6weight percent.

In one embodiment, the cover layer composition further comprises atleast one UV absorber and/or light stabilizer, preferably hindered aminelight stabilizer, to prevent significant yellowing from unsaturatedcomponents contained therein, and to prevent cover surface fractures dueto photo-degradation. These UV absorbers and light stabilizers areparticularly useful in visible cover layers, such as the outer coverlayer, or any other internal layer when the layer(s) disposed about itare translucent or transparent. Suitable UV absorbers include Uvinul®DS49 (disodium 2,2′-dihydroxy-4,4′-dimethyoxy-5,5′-disulfobenzophenone)and Uvinul® DS50 (2,2′,4,4′-tetrahydroxy-benzophenone) by BASFCorporation; Tinuvin® 328(2-(2′-hydroxy-3′,5′-di(t-amylphenyl)benzotriazole), Tinuvin® 571(2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol), Tinuvin® P(2-(2-hydroxy-5-methylphenyl)benzotriazole), and CGL 1545 (experimentaltriazine derivative) by Ciba Specialty Chemicals Corporation; Sanduvor®PR-25 (dimethyl-4-methoxy-benzylidenemalonate) by Clariant Corporation;Cyasorb® UV-2337 (2-(2′-hydroxy-3′,5′-di(t-amylphenyl)benzotriazole),Cyasorb® UV-1164(2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-octyloxyphenol),and Cyasorb® UV-3638 (2,2′-(1,4-phenylene)-bis(4-3,1-benzoxazin-4-one))by Cytec Industries; Quercetin® (3,3′,4′,5,7-pentahydroxy flavone) by EMIndustries; UV-Chek® AM-300 (2-hydroxy-4-n-octyloxy-benzophenone) andUV-Chek® AM-340(2,4-di(t-butylphenyl)-3,5-di(t-butyl)-4-hydroxybenzoate) by FerroCorporation; Maxgard® DPA-8 (2-ethylhexyl-2-cyano-3,3-diphenylacrylate)by Garrison Industries; Givsorb® 2 (propanedione), Givsorb® 13, Givsorb®14, and Givsorb® 15 by Givaudan-Roure Corporation; Norbloc® 6000(2-(2′-hydroxy-5′-(2-hydroxyethyl)benzotriazole) and Norbloc® 7966(2-(2′-hydroxy-5′-methacryloxyethylphenyl)-2H-benzotriazole) by JessenPharmaceuticals. Suitable light stabilizers include, but are not limitedto, Tinuvin® 622LD (dimethyl succinate polymer with4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol) and Tinuvin® 765(bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate) by Ciba SpecialtyChemicals Corporation; Sanduvor® 3070 (hindered amine) by ClariantCorporation; Cyasorb® UV-3581(3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidylpyrrolidin-2,5-dione) byCytec Industries. For aromatic and unsaturated formulations, thepreferred UV absorber is Tinuvin® 328, and the preferred hindered aminelight stabilizer is Tinuvin® 765. A preferred light stabilizer forsaturated formulations is Tinuvin® 292. In addition, Tinuvin® 213 and770, and antioxidants to prevent degradation of the cover composition,such as Irganox® 1010(tetrakis(3,5-di(t-butyl-hydroxyhydrocinnamate))methane) and Irganox®1135 (C₇₋₉-branched alkyl ester of 3,5-di(t-butyl-4-hydroxyhydrocinnamicacid) by Ciba Specialty Chemicals Corporation and Sandostab® P-EPQ (arylphosphonite) by Clariant Corporation, are also applicable.

Other additive for the cover layer compositions of the present inventioninclude, but are not limited to, accelerators to speed up thepolymerization reaction, fillers to adjust density and/or modulus of thelayer, viscosity modifiers, release agents, plasticizers,compatibilizing agents, coupling agents, dispersing agents, colorantsincluding pigments and dyes, optical brighteners, surfactants,lubricants, stabilizers, metals, processing aids or oils to affectrheological and mixing properties, blowing agents, and any othermodifying agents known to one of ordinary skill in the art. Pigments maybe fluorescent, autofluorescent, luminescent, or chemoluminescent, andinclude white pigments such as titanium oxide and zinc oxide. Theseadditives may be blended into the cover layer composition in amountssufficient to achieve their specific purposes and desired effects.

As used herein, the term “filler” refers to any compound or compositionthat can be used to vary certain properties of selected portions of thegolf ball, including density or specific gravity, flexural modulus,tensile modulus, strength, moment of inertia, hardness, abrasionresistance, weatherability, volume, weight, etc. The fillers arepreferably in the forms of nano-scale or micro-scale powders, fibers,filaments, flakes, whiskers, wires, tubes, or particulates forhomogenous dispersion. Suitable fillers for golf balls may be solid orhollow, and include, for example, metal (or metal alloy) powder, metaloxide and salts, ceramics, particulates, carbonaceous materials,polymeric materials, glass microspheres, and the like or blends thereof.Non-limiting examples of metal (or metal alloy) powders include, but arenot limited to, bismuth, brass, bronze, cobalt, copper, inconel, iron,molybdenum, nickel, stainless steel, titanium, aluminum, tungsten,beryllium, zinc, magnesium, manganese, and tin. Non-limiting examples ofmetal oxides and salts include, but are not limited to, zinc oxide, ironoxide, aluminum oxide, titanium dioxide, magnesium oxide, zirconiumoxide, tungsten trioxide, zirconium oxide, tungsten carbide, tungstenoxide, tin oxide, zinc sulfide, zinc sulfate, zinc carbonate, bariumsulfate, barium carbonate, calcium carbonate, calcium metasilicate,magnesium carbonate, and silicates. Non-limiting examples ofcarbonaceous materials include graphite and carbon black. Examples ofother useful fillers include precipitated hydrated silica, boron, clay,talc, glass fibers, aramid fibers, mica, diatomaceous earth, regrind(typically recycled core material mixed and ground to 30 mesh particlesize). Examples of polymeric materials include, but are not limited to,hollow spheres or microspheres of chemically or physically foamedthermoplastic or thermosetting polymers, such as epoxies, urethanes,polyesters, nucleated reaction injection molded polyurethanes orpolyureas.

Conventional materials for golf ball cover, intermediate layer, or corethat may be blended with the polyurethane, polyurea, or hybridcompositions of the present invention, by about 1 weight percent toabout 95 weight percent of the composition, include:

-   1) Non-ionomeric acid polymers, such as copolymers E/Y of an olefin    E having 2 to 8 carbon atoms and a carboxylic acid Y having 3 to 8    carbon atoms, or terpolymers E/X/Y having an additional softening    comonomer X. The olefin E is preferably ethylene, and the acid Y    includes acrylic, methacrylic, crotonic, maleic, fumaric, or    itaconic acid. The comonomer X includes vinyl esters of aliphatic    carboxylic acids having 2 to 10 carbon atoms, and alkyl ethers,    alkyl acrylates, or alkyl alkylacrylates of alkyl groups having 1 to    10 carbon atoms. Depending on the acid content by weight, the    polymer may be referred to as low acid (about 2% to less than 10%),    medium acid (about 10% to less than 16%), and high acid (about 16%    to about 50%). The comonomer, when present, may be in an amount of    about 2% to about 40% by weight of the acid polymer. Preferred    non-ionomeric acid polymers include Nucrel® from E. I. DuPont de    Nemours & Company and Escor® from ExxonMobil.-   2) Anionic and cationic ionomers such as the acid polymers above    partially or fully neutralized with organic or inorganic cations,    such as zinc, sodium, lithium, magnesium, potassium, calcium,    manganese, nickel, ammonium (primary, secondary, tertiary), or the    like. The extent of neutralization ranges from about 0% to about    100% or more, preferably at least about 50%, more preferably at    least about 70%. Preferred acid ionomers include Surlyn® from E. I.    DuPont de Nemours & Company and Iotek® from ExxonMobil.-   3) Thermoplastic or thermoset (vulcanized) synthetic or natural    rubbers, including polyolefins and copolymers or blends thereof,    such as balata, polyethylene, polypropylene, polybutylene, isoprene    rubber, ethylene-propylene rubber, ethylene-butylene rubber,    ethylene-propylene-(non-conjugated diene) terpolymers; polystyrenes    and copolymers thereof, such as styrene-butadiene copolymers,    poly(styrene-co-maleic anhydride), acrylonitrile-butylene-styrene    copolymers, poly(styrene sulfonate); and homopolymers or copolymers    produced using single-site catalyst such as metallocene (grafted or    non-grafted).-   4) Polyphenylene oxide resins, polyarylene ethers, or blends of    polyphenylene oxide with high impact polystyrene such as Noryl® from    General Electric Company.-   5) Polyurethanes prepared from polyols and diisocyanates or    polyisocyanates, including thermoplastic polyurethanes, thermoset    polyurethanes, and polyurethane ionomers.-   6) Polyurea such as thermoplastic polyurea, thermoset polyurea,    polyurea ionomers, and include those disclosed in U.S. Pat. No.    5,484,870 and U.S. patent application Ser. Nos. 10/072,395 and    10/228,311, all of which are incorporated herein by reference in    their entirety.-   7) Aliphatic and/or aromatic thermoplastics, including polyesters,    such as ethylene methylacrylate, ethylene ethylacrylate, ethylene    vinyl acetate, poly(ethylene terephthalate), poly(butylene    terephthalate), poly(propylene terephthalate), poly(trimethylene    terephthalate), modified poly(ethylene terephthalate)/glycol,    poly(ethylene naphthalate), cellulose esters, Hytrel® from E. I.    DuPont de Nemours & Company, and Lomod® from General Electric    Company; polycarbonates; polyacetals; polyimides; polyetherketones;    polyamideimides; thermoplastic block copolymers (Kraton® rubbers    from Shell Chemical); co-polyetheramides (Pebax® from AtoFina); and    elastomers in general.-   8) Vinyl resins such as polyvinyl alcohols, polyvinyl alcohol    copolymers, polyvinyl chloride, block copolymers of alkenyl    aromatics with vinyl aromatics and polyesteramides, copolymers of    vinyl chloride with vinyl acetate, acrylic esters or vinylidene    chloride.-   9) Polyamides such as poly(hexamethylene adipamide) and others    prepared from diamines, fatty acids, dibasic acids, and amino acids    (poly(caprolactam)), and blends of polyamides with Surlyn®, ethylene    homopolymers or copolymers or terpolymers, etc.-   10) Acrylic resins and blends of these resins with polyvinyl    chloride or other elastomers.-   11) Blends and alloys, including blends of polycarbonate and    acrylonitrile-butylene-styrene, blends of polycarbonate and    polyurethane, blends of polyvinyl chloride with    acrylonitrile-butadiene-styrene or ethylene vinyl acetate or other    elastomers, blends of thermoplastic rubbers with polyethylene or    polypropylene.    Preferably, a thermoplastic polyurethane, polyurea, or    polyurethane/polyurea hybrid of the present invention is blended    with one or more thermoplastic materials listed above to form a    thermoplastic composition for a golf ball portion.

The cover layer may be formed from a thermoplastic or thermosetpolyurethane or polyurea, such as the ones disclosed herein. Preferablythe polyurethane or polyurea is saturated. The cover layer may have aWVTR of less than about 2 g/(m²×day), a modulus of about 1,000 to about100,000 psi, a material hardness of less than about 90 Shore D, morepreferably less than about 70 Shore D, and a hardness as measured on theball of less than about 80 Shore D. In one embodiment, the cover layerhas a Shore D hardness of about 30 to about 70 and a modulus of about10,000 psi to about 80,000 psi. The cover layer may have any thicknessof less than about 0.5 inches, preferably thin with a thickness of lessthan about 0.05 inches, more preferably about 0.005 inches to about 0.03inches. Alternatively, the cover layer is relatively thick, about 0.05inches to about 0.2 inches, preferably about 0.05 inches to about 0.1inches. The cover layer preferably has an inner diameter of about 0.5inches to about 1.7 inches, and an outer diameter of about 0.7 inches toabout 1.8 inches. The golf ball compression is preferably less thanabout 100.

Any method known to one of ordinary skill in the art may be used toproduce the cover layer of the present invention. One-shot methodinvolving concurrent mixing of the isocyanate, the polyether polyahl,and the curing agent is feasible, but the resulting mixture isnon-homogenous and difficult to control. The prepolymer method describedabove is most preferred, because it affords a more homogeneous mixtureresulting in a more consistent polymer composition. The prepolymer maybe reacted with a diol or a secondary diamine to form a thermoplasticmaterial, or reacted with a triol, tetraol, primary diamine, triamine,or tetramine to form a thermoset material. Other methods suitable forforming the layers include casting, compression molding, reactioninjection molding (“RIM”), liquid injection molding (“LIM”),injection-compression molding, pre-reacting the components to form aninjection moldable thermoplastic material and then injection molding,and combinations thereof, such as RIM/compression molding,injection/compression molding, progressive compression molding, and thelike. Thermoplastic formulations may be processed using any number ofcompression or injection molding techniques. Thermoset formulations maybe castable, reaction injection moldable, sprayable, or applied in alaminate form or by any techniques known in the art. Castable reactiveliquid materials such as polyurea, polyurethane, andpolyurethane/polyurea hybrid can provide very thin layers such as outercover layers that are desirable on golf balls. Other techniques includespraying, dipping, spin coating, or flow coating methods.

The core of the golf balls in the present invention may be solid,fluid-filled, gel-filled, or gas-filled. The solid core can be made fromany suitable core materials including thermoset plastics, such asnatural rubber, polybutadiene, polyisoprene, styrene-butadiene orstyrene-propylene-diene rubber, and thermoplastics such as ionomerresins, polyamides, polyesters, or a thermoplastic elastomer. Suitablethermoplastic elastomers include Pebax® from AtoFina Chemicals Inc.,Hytrel® from E.I. Du Pont de Nemours and Company, thermoplastic urethanefrom various manufacturers, and Kraton® from Shell Chemical Company. Thecore materials can also be formed from a castable material. Suitablecastable materials include polyurethanes, polyureas, epoxies, silicones,etc. Additionally, suitable core materials may also include a RIMpolyurethane or polyurea, preferably the nucleated versions wherenitrogen gas is whipped into the reaction mixture prior to injectioninto a closed mold to form the layer.

Preferred compositions for solid cores include a base rubber, acrosslinking agent, and an initiator. The base rubber typically includesnatural or synthetic rubbers. A preferred base rubber is1,4-polybutadiene having a cis-bond of at least about 40%, a Mooneyviscosity of at least about 30, a molecular weight of at least about150,000, and a polydispersity of less than about 4. Examples ofdesirable polybutadiene rubbers include Buna® CB22 and CB23 from Bayer,Ubepol® 360L and 150L from Ube Industries, and Cariflex® BCP820 andBCP824 from Shell Chemical. Blends of two or more such polybutadienesare desirable for the solid cores. In one embodiment, a cobalt or nickelcatalyzed polybutadiene having a Mooney viscosity of from about 50 toabout 150 is mixed with a neodymium catalyzed polybutadiene having aMooney viscosity of from about 30 to about 100. The weight ratio betweenthe two polybutadienes may range between about 5:95 and 95:5. Thepolybutadiene can also be mixed with other elastomers known in the art,such as natural rubber, polyisoprene rubber and/or styrene-butadienerubber, in order to modify the properties of the core.

Suitable cross-linking agents for the polybutadiene-based solid coresinclude metal salts of unsaturated fatty acid having 3 to 8 carbonatoms, such as diacrylate, dimethacrylate, and monomethacrylate, whereinthe metal can be magnesium, calcium, zinc, aluminum, sodium, lithium ornickel. Preferred acrylates include zinc diacrylate, zincdimethacrylate, and blends thereof. Zinc diacrylate is preferred becauseit provides golf balls with a high initial velocity, but the presentinvention is not limited thereto. The crosslinking agent is typicallypresent in an amount of at least about 10 parts per hundred (“pph”)parts of the base polymer, preferably from about 20 pph to about 40 pphof the base polymer.

The peroxide initiators used to promote the cross-linking reaction inthe core are well known in the art, and can be any known peroxides orblends thereof that decompose during the cure cycle. Suitable peroxideinitiators include organic peroxide compounds, such as dicumyl peroxide,1,1-di(t-butylperoxy) 3,3,5-trimethyl cyclohexane, α,α-bis(t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5 di(t-butylperoxy)hexane, di-t-butyl peroxide, and blends thereof. Commercially availableexamples include, but are not limited to, Varox® 231XL and DCP-R fromAtoFina, Perkadox® BC and 14 from Akzo Nobel, and Elastochem® DCP-70from Rhein Chemie. In their pure forms, the initiators are present in anamount of at least about 0.25 pph of the base polymer, preferablybetween about 0.5 pph and about 2.5 pph. It is understood to one skilledin the art to adjust the amount of the initiators according to theiractivity and concentration.

In polybutadiene-based solid cores of the present invention, it ispreferred to blend in a halogenated organosulfur compound such as ahalogenated thiophenol or a metal salt thereof to further enhance thesoftness and resiliency of the core. The halogenated thiophenol,preferably pentachlorothiophenol (“PCTP”) or ZnPCTP, function in part asa cis-to-trans catalyst that convert some cis-1,4 bonds in thepolybutadiene into trans-1,4 bonds. The utilization of halogenatedorganosulfur compounds like PCTP and ZnPCTP in golf balls to producesoft and fast cores is disclosed in co-pending U.S. patent applicationSer. No. 09/951,963, which is incorporated by reference herein in itsentirety. PCTP is available under the tradename of Struktol® fromStruktol Company of America, and ZnPCTP is available from eChinaChem.The halogenated organosulfur compounds are present in an amount of atleast about 0.1 pph of the base rubber, preferably about 0.1 pph toabout 2 pph; alternatively the amount of halogenated organosulfurcompound used is at least about 2 pph, preferably about 2.3 pph to about5 pph.

The solid core may also include fillers to adjust hardness, strength,modulus, weight, density and/or specific gravity of the core. Suitablefillers include metal or alloy powders, metal oxides and salts,ceramics, particulate, carbonaceous materials, polymeric materials,glass microspheres, and the like or blends thereof. These fillers may behollow, solid, filled, unfilled, surface treated, or non-surfacetreated. Specific fillers for the core include tungsten powder, tungstencarbide, zinc oxide, tin oxide, tungsten oxide, barium sulfate, zincsulfate, barium carbonate, calcium carbonate, zinc carbonate, an arrayof silica and clay, regrind (recycled core material typically ground toabout 30 mesh particle), and high-Mooney-viscosity rubber regrind.

Other optional additives for the golf ball core are well known in theart, and may be blended into the core in amounts sufficient to achievetheir specific purposes and desired effects. Such additives includeantioxidants to prevent the breakdown of the base polymer, acceleratorsto speed up the polymerization reaction, processing aids or oils toaffect rheological and mixing properties, foaming agents, cis-to-transcatalysts, adhesives, coupling agents, stable free radicals, radicalscavangers, scorch retarders, and blends thereof.

The core of the golf ball of the present invention has a diameter of atleast about 0.5 inches. In one embodiment, the core diameter is at leastabout 1 inches, more preferably from about 1.5 inches to about 1.65inches, and most preferably from about 1.55 inches to about 1.6 inches.The core may have a compression of from about 20 to about 120, morepreferably from about 30 to about 100, and most preferably from about 40to about 80. Alternatively, the core may be very soft, with acompression of less than about 20. The core should also be highlyresilient, having a COR of preferably at least about 0.7, morepreferably at least about 0.75, and most preferably at least about 0.8.Conventional methods and techniques may be used to form the solid coresfrom the base compositions disclosed herein.

An optional intermediate layer may be disposed between the core and thecover. The intermediate layer may be part of the core as an outer corelayer, or part of the cover as an inner cover layer. The intermediatelayer of the golf ball may be made of any core or cover compositionsdisclosed herein. Alternatively, the intermediate layer may comprisenon-ionomeric acid polymers or ionomeric derivatives thereof,polyamides, polyolefins, polyurethanes, polyurea, cast or RIMpolyurethanes or polyurea, epoxies, polyesters, polyetheresters such asHytrel® from DuPont, polyetheramides such as Pebax® from AtoFina,nylons, single-site catalyzed polymers, metallocene-catalyzed polymers,poly(ethylene terephthalate), poly(butylene terephthalate),poly(propylene terephthalate), poly(trimethylene terephthalate),poly(ethylene naphthalate), polystyrene polymers, poly(styrene-co-maleicanhydride), functionalized styrene-butadiene elastomers, styrenic blockcopolymers such as Kraton® from Shell Chemicals,acrylonitrile-butadiene-styrene copolymers (“ABS”), poly(styrenesulfonate), polyethylene styrene, grafted polypropylenes, graftedpolyethylenes, polyvinyl chlorides, grafted polyvinyl chlorides,polyvinyl acetates having less than about 9% of vinyl acetate by weight,polycarbonates, blends of polycarbonate andacrylonitrile-butadiene-styrene, blends of polycarbonate andpolyurethane, polyvinyl alcohols, polyvinyl alcohol copolymers,polyethers, polyarylene ethers, polyphenylene oxides, block copolymersof alkenyl aromatics with vinyl aromatics, polyesteramides, polyamides,polyimides, polyetherketones, polyamideimides, silicone, and metal saltsof fatty acids. Two or more of these materials may be blended togetherto form the intermediate layer.

In one embodiment, the intermediate layer is a continuous layer formedfrom one or more non-ionomeric acid polymers and/or ionomers derivedtherefrom. The non-ionomeric acid polymer may be an E/Y copolymer orE/X/Y terpolymer, where E is an olefin, Y is a carboxylic acid, and X isa softening comonomer. Preferably, the olefin is ethylene and thecarboxylic acid is acrylic acid, methacrylic acid, crotonic acid, maleicacid, fumaric acid, itaconic acid, or a combination thereof. Thesoftening comonomer is preferably vinyl esters of aliphatic carboxylicacids where the acids have 2 to about 10 carbon atoms, or alkyl ethers,alkyl acrylates, or alkyl alkylacrylates where the alkyl groups have 1to about 10 carbon atoms. The copolymer or terpolymer preferably has anacid content of from about 1% to about 50% by weight, and the terpolymerpreferably has a comonomer content of about 2% to about 40%. The acidpolymer preferably has a melt flow rate of about 0.1 g/10-min to about500 g/10-min, a flexural modulus of about 5,000 psi to about 80,000 psi,a Shore D material hardness of about 20 to about 80, and a WVTR of about0.01 to about 0.9 g/(m²*day) at 38° C. and 90% relative humidity.Specific examples of the non-ionomeric acid copolymer includeethylene/acrylic acid copolymers (“EAA”) and ethylene/methacrylic acidcopolymers (“EMAA”). Examples of the non-ionomeric acid terpolymer areethylene/methyl acrylate/acrylic acid terpolymers (“EMAAA”),ethylene/n-butyl acrylate/methacrylic acid terpolymers, andethylene/isobutyl acrylate/methacrylic acid terpolymers. Commercially,EAA resins are available from Dow Chemical under the trade name ofPrimacor® and from ExxonMobil Chemical under the trade name of Escor®,EMAA resins are available from E. I. du Pont de Nemours and Companyunder the trade name of Nucrel®, and EMAAA resins are available fromExxonMobil Chemical under the trade name of Escor® AT.

The non-ionomeric acid polymers disclosed herein may be converted toacid ionomers through partial or full neutralization with a organic orinorganic cation such as sodium, lithium, potassium, zinc, magnesium,calcium, or ammonium. Preferred ionomers include high-acid ionomers,high-flow ionomers, high crystalline ionomers, and blends thereof.High-acid ionomers are anionic copolymers or terpolymers having an acidcontent of at least about 16% by weight. At least about 10% by weight ofthe carboxylic acid groups are neutralized with a metal cation.Preferably, between about 30% and about 100% of the carboxylic acidgroups are neutralized. High-acid ionomers are commercially availablefrom several different manufacturers. For example, ionic copolymers ofethylene and methacrylic acid are produced by E. I. DuPont de Nemours &Company under the trademark of Surlyn®, ionic copolymers and terpolymersof ethylene and acrylic acid are produced by ExxonMobil Chemical underthe trademarks of Escor® and Iotek®, filler-modifiedpoly(ethylene-methacrylic acid) ionomers are produced by DuPont underthe trademark of Bexloy®, ionomeric polyethylene copolymers are producedby A. Schulman Inc. under the trademark of Formion®, and polyolefinionomers are produced by Diamond & Network Polymers, Inc.

The intermediate layer may incorporate a filler to attain preferredphysical and mechanical properties. Preferably, the filler is amodulus-enhancing filler, including tungsten, tungsten oxide, bariumsulfate, carbon black, silica, titanium oxide, or a blend thereof.Preferably, the amount of the fillers in the composition ranges fromabout 5% to about 70% by weight, more preferably from about 10% to about50% by weight. The composition of the intermediate layer may have amodulus of about 1,000 psi to about 150,000 psi, a material hardness ofabout 20 Shore C to about 80 Shore D, a thickness of about 0.005 inchesto about 0.6 inches, and a hardness as measured on the golf ball of lessthan about 80 Shore D. The intermediate layer preferably has an outsidediameter in the range of 70% to 98% of the finished ball diameter and aninner diameter in the range of 30% to 90% of the finished ball diameter.Alternatively, the intermediate layer may have an inner diameter ofabout 0.5 inches to about 1.6 inches, and an outside diameter of about 1inches to about 1.65 inches. To prevent or minimize the penetration ofmoisture, typically water vapor, into the core, the intermediate layerpreferably has a WVTR lower than that of the cover. More preferably, theWVTR of the intermediate layer is no greater than that of an ionomerresin such as Surlyn®, which is in the range of about 0.45 g/(m²×day) toabout 0.95 g/(m²×day).

The composition of the intermediate layer may be applied as a liquid,powder, dispersion, lacquer, paste, gel, melt, or solid half shells. Theintermediate layer may be formed around the core or onto the inside ofthe cover by sheet stock or vacuum shrink-wrapping, compression molding,injection molding, vacuum deposition, RIM, lamination, casting,spraying, dipping, powder coating, or any other deposition means.Preferably, a combination of these methods is used, such asinjection/compression molding, RIM/compression molding,pre-form/compression molding, injection molding/grinding,injection/progressive compression molding, or co-injection molding. Asimplified casting method using a single block material to produce theintermediate layer can be utilized to make any castable components ofthe golf ball, including any intermediate layer, the innermost core orany portion of the cover.

The resulting golf ball, including the core, the intermediate layer andthe cover as described above, preferably has a COR of greater than about0.7, and more preferably greater than about 0.8. The golf ballpreferably has an Atti compression of at least about 30, more preferablyfrom about 50 to about 120, and most preferably from about 50 to about90. The golf ball preferably has an overall diameter of at least about1.68 inches, more preferably from about 1.68 inches to about 1.76inches. The golf ball further has a dimple coverage on its outermostsurface of greater than about 60%, preferably greater than about 70%.Preferred dimple patterns involving catenary curves, and preferred liftand drag characteristics of the golf ball of the present invention aredisclosed in co-pending U.S. application Ser. Nos. 09/989,191 and10/096,852, respectively, both incorporated herein by reference in theirentirety.

Golf balls of the present invention may have a variety of constructions,typically comprising at least a core and a cover. Optionally, one ormore intermediate layers may be disposed between the core and the cover;the core may be a single solid mass, or include a solid, liquid-filled,gel-filled or gas-filled center and one or more outer core layers; andthe cover may include an outer cover layer and one or more inner coverlayers. Any of the outer core layers, the intermediate layers, or theinner cover layers may be a continuous layer, a discontinuous layer, awound layer, a molded layer, a lattice network layer, a web or net, anadhesion or coupling layer, a barrier layer, a layer of uniformed ornon-uniformed thickness, a layer having a plurality of discrete elementssuch as islands or protrusions, a solid layer, a metallic layer, aliquid-filled layer, a gas-filled layer, or a foamed layer.

The material compositions of the present invention and their applicationin golf balls are further illustrated in the following non-limitingexamples. Specifically, twenty-four golf ball subassemblies of the samecomposition and construction are divided evenly into a control group andan example group. Each subassembly is formed of a polybutadiene-basedsolid core of about 1.55 inches in diameter encapsulated within anionomer-based mantle layer of about 0.035 inches in thickness, so thatthe subassembly has a diameter of about 1.62 inches. Castable covers ofabout 0.03 inches in thickness are formed onto the subassemblies usinginjection molding. The golf balls of the control group are Pro V1® golfballs commercially available from Titleist. The respective coverformulations of the control group and the example group, the physicalproperties of the resulting golf balls, and their performancecharacteristics are measured and reported in Table I below.

TABLE I Control Example Cover Formulation Polyurethane PolyurethanePolyol PTMEG 2000 PTG-L 2000 Isocyanate Content 6% NCO (MDI) 7.9% NCO(H₁₂MDI) Curing Agent Ethacure ® 300 Clearlink ® 1000 PhysicalProperties Material Hardness 45 Shore D 53 Shore D Hardness (on theball) 58 Shore D 63 Shore D Weight 1.603 1.602 Compression 89 91Performance Data COR at 125 ft/s 0.811 0.809 QUV 8-day ΔYI (Δb*) 82.2(30.9) 0.4 (0.2)

Both the controls and the samples comprised a solid polybutadiene coreof about 1.55 inches in diameter, a Surlyn® ionomer-based intermediatelayer of about 0.035 inches thick, and a cover of about 0.03 inchesthick. The final golf balls had a size of about 1.68 inches in diameter.The 8-day accelerated weathering test (QUV) simulating outdoor exposureto moisture and sunlight entailed cycling the finished golf ballsbetween 4-hour illumination periods under a UV-340a lamp at anirradiance power of 1.00 W/m²/nm and an air temperature of 50° C., and4-hour dark periods at an air temperature of 40° C. The covers weretested for changes in yellow index (“ΔYI”) according to ASTM G53-88 (nowreplaced with ASTM G154-00), and changes in perceptual yellowness(“Δb*”) according to CIELAB. The cover formulation of the controls wasunsaturated, comprising a prepolymer of 6% NCO, formed frompolytetramethylene glycol (molecular weight of about 2,000) and4,4′-diphenylmethane diisocyanate (MDI). Consequently both ΔYI and Δb*were large. In comparison, the cover formulation of the samples used asaturated composition of the present invention, comprising a prepolymerof 8% NCO, formed from a copolymer of tetrahydrofuran and2-methyl-tetrahydrofuran (molecular weight of about 2,000) and4,4′-dicyclohexylmethane diisocyanate (H₁₂MDI). Besides being harder,the sample cover displayed much better light stability (smaller ΔYI andΔb*) than the controls.

The compositions for golf ball portions as disclosed herein may be usedin sporting equipment in general. Specifically, the compositions may beapplied in various game balls, golf club shafts, golf club head inserts,golf shoe components, and the like.

All patents and patent applications cited in the foregoing text areexpressly incorporated herein by reference in their entirety.

The invention described and claimed herein is not to be limited in scopeby the specific embodiments herein disclosed, since these embodimentsare intended solely as illustrations of several aspects of theinvention. Any equivalent embodiments and various modifications apparentto those skilled in the art are intended to be within the scope of thisinvention. It is further understood that the various features of thepresent invention can be used singly or in combination thereof. Suchmodifications and combinations are also intended to fall within thescope of the appended claims.

1. A golf ball comprising a core and a cover, wherein the core or thecover comprises a thermoplastic or thermoset composition comprising apolyurea prepolymer formed from: a reactant A comprising an isocyanate;and a reactant B comprising a polyamine having a polydispersity of 3 orless, the polyamine being a polyether polyamine comprising a repeatingbranched oxyalkylene monomer unit

where Y₁ is a hydrocarbon; Y₂, Y₃, and Y₄ are independently hydrogen orhydrocarbons; a, b, and x are independent whole numbers of 0 to about10; and at least one of a, b, and x is an integer of 1 to about 10 or apolymerized polyamine formed from a chiral diol

or a cyclic ether

where R₁ is a linear or branched hydrocarbon of 1 to about 10 carbonatoms; R₂ is a hydrocarbon of 1 to about 10 carbon atoms, or hydrogenwhen R₁ is a branched hydrocarbon; R₃ is hydrogen or a linear orbranched hydrocarbon of 1 to about 10 carbon atoms; and R₄ is a linearor branched hydrocarbon of 1 to about 10 carbon atoms.
 2. The golf ballof claim 1, wherein reactant B is the polymerized polyamine, thepolymerized polyamine being is formed from a copolymerization of achiral diol and a second diol or cyclic ether having about 2 carbonatoms to about 20 carbon atoms.
 3. The golf ball of claim 2, wherein thechiral diol comprises 2-methyl-1,4-butanediol, and the second diol orcyclic ether comprises 1,4-butanediol or tetrahydrofuran.
 4. The golfball of claim 1, wherein reactant B is the polymerized polyamine, thepolymerized polyamine being formed from a copolymerization of a chiralcyclic ether and a second diol or cyclic ether having about 2 carbonatoms to about 20 carbon atoms.
 5. The golf ball of claim 4, wherein thechiral cyclic ether comprises 2-methyl-tetrahydrofuran, and the seconddiol or cyclic ether comprises 1,4-butanediol or tetrahydrofuran.
 6. Thegolf ball of claim 1, wherein the reactant B is a substantiallynon-crystalline block co-polyether polyamine having a melting point ofless than about 15° C.
 7. The golf ball of claim 1, wherein reactant Bhas a molecular weight of about 500 to about 10,000.
 8. The golf ball ofclaim 1, wherein reactant A is an organic, modified organic, aliphatic,alicyclic, unsaturated, araliphatic, aromatic, substituted, orunsubstituted isocyanate, comprising isocyanate-containing monomers,dimers, trimers, multimeric adducts, oligomers, polymers, prepolymers,low-free-monomer prepolymers, quasi-prepolymers, diisocyanates,polyisocyanates, uretdiones, isocyanurates, or blends thereof.
 9. Thegolf ball of claim 1, wherein an equivalent ratio of reactant B toreactant A is about 0.01:1 to about 1:1, and the polyurea prepolymer hasa NCO content of less than about 15 percent.
 10. The golf ball of claim1, wherein the composition further comprises a curing agent comprisingsaturated or unsaturated monomeric polyahls, oligomeric polyahls,polyether polyahls, polyester polyahls, polycaprolactone polyahls,polycarbonate polyahls, polyhydrocarbon polyahls, polyamide polyahls,polyolefin polyahls, polyahls converted from acid functional oligomersor polymers or ionomers thereof, diols, triols, tetraols, polyols,diamines, triamines, tetramines, polyamines, amine- andhydroxy-containing hybrid compounds, or epoxies; and wherein anequivalent ratio of the polyurethane prepolymer to the curing agent isabout 1:0.6 to about 1:1.5.
 11. The golf ball of claim 1, wherein thecomposition is substantially saturated.
 12. The golf ball of claim 1,wherein the composition has a material hardness of less than about 70Shore D.
 13. The golf ball of claim 1, wherein the golf ball has acompression of less than about
 100. 14. The golf ball of claim 1,wherein the golf ball further comprises an intermediate layer disposedbetween the core and the cover, the intermediate layer comprisingionomers, elastomers, or acid copolymers or terpolymers having an acidcontent of about 2% to about 50% and being neutralized by about 0% toabout 100%.
 15. The golf ball of claim 1, wherein the cover comprises anouter cover layer and an inner cover layer, at least one of the coverlayers is formed from a polyurethane or polyurea composition having aShore D hardness of about 30 to about 70 and a flexural modulus of about10,000 psi to about 80,000 psi.
 16. A golf ball comprising a core, acover, and an intermediate layer disposed between the core and thecover, wherein at least one of the core, the intermediate layer, or thecover comprises a thermoplastic or thermoset composition formed from: anisocyanate; and a polymerized polyahl comprising an amine-terminatedpoly(tetrahydrofuran-co-methyltetrahydrofuran).
 17. The golf ball ofclaim 16, wherein the amine-terminatedpoly(tetrahydrofuran-co-methyltetrahydrofuran) has a structure of:

where R₅ is —CH₂—CH₂—CH₂—CH₂—; R₆ is —CH₂—CH(CH₃)—CH₂—CH₂—,—CH₂—CH₂—CH(CH₃)—CH₂—, —O—CH(CH₃)—CH₂—CH₂—CH₂—, or—O—CH₂—CH₂—CH₂—CH(CH₃)—; and m, n, and z are independent integers of 1to about
 100. 18. The golf ball of claim 16, wherein theamine-terminated poly(tetrahydrofuran-co-methyltetrahydrofuran) has amolecular weight of about 1,000 to about 5,000, the amine-terminatedpoly(tetrahydrofuran-co-methyltetrahydrofuran) and the isocyanate formsa polyurea prepolymer having an NCO content of about 4% to about 15%,the core has a diameter of about 1.5 inches to about 1.65 inches and acompression of about 30 to about 120 and a coefficient of restitution of0.75 or greater, the cover has a Shore D hardness of about 30 to about70 and a thickness of about 0.005 inches to about 0.1 inches, and thegolf ball has a compression of about 30 to about 120 and a dimplecoverage of about 70% or greater.
 19. A golf ball comprising a core anda cover, the cover comprising a thermoplastic or thermoset compositioncomprising a polyamine, wherein the polyamine comprises a repeatingoxyalkylene unit

where Y₁ is a hydrocarbon, Y₂, Y₃, and Y₄ are independently hydrogen orhydrocarbons, a, b, and x are independent whole numbers of 0 to about10, and at least one of a, b, and x is an integer of 1 to about 10 orthe polyamine is formed from a diol

or a cyclic ether

where R₁ is a linear or branched hydrocarbon of 1 to about 10 carbonatoms, R₂ is a hydrocarbon of 1 to about 10 carbon atoms, or hydrogenwhen R₁ is a branched hydrocarbon, R₃ is hydrogen or a linear orbranched hydrocarbon of 1 to about 10 carbon atoms, and R₄ is a linearor branched hydrocarbon of 1 to about 10 carbon atoms.
 20. The golf ballof claim 19, wherein the polyamine has a polydispersity of about 3 orless.
 21. The golf ball of claim 19, wherein the polyamine has at leastone property that fluctuates by about 10% or less in a temperature rangeof about −20° C. to about 20° C., the property being material hardness,flexural modulus, elastic modulus, storage modulus, elongation, tensilestrength, tear strength, or compression.
 22. The golf ball of claim 19,wherein the polyamine further comprises a second repeating linearoxyalkylene unit.
 23. The golf ball of claim 19, wherein the polyaminehas an amine number of about 10 to about
 150. 24. The golf ball of claim19, wherein the cover comprises an outer cover layer comprising thecomposition, and an intermediate layer disposed between the core and theouter cover layer.
 25. The golf ball of claim 19, wherein the covercomprises an outer cover layer, and an intermediate layer comprising thecomposition and being disposed between the core and the outer coverlayer.
 26. The golf ball of claim 19, wherein the composition furthercomprises a polyisocyanate and a hindered secondary diamine.
 27. Thegolf ball of claim 19, wherein the composition is substantiallysaturated.